• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    use of an amino acid zinc halide complex, composition comprising an amino acid zinc halide complex and method of cleaning a tooth described herein are methods of cleaning a tooth comprising administering a composition comprising a zinc halide complex amino acid in the oral cavity; and retaining the composition in the oral cavity for a time sufficient to form a precipitate.
    公开号:BR112015014444B1
    申请号:R112015014444-6
    申请日:2012-12-19
    公开日:2019-10-01
    发明作者:Zhiqiang Liu；Long Pan；Shaotang Yuan；Jairajh Mattai；James G. Masters
    申请人:Colgate-Palmolive Company；
    IPC主号:
    专利说明:

    1/23
    USE OF AN AMINO ACID ZINC HALOGENIDE COMPLEX, COMPOSITION THAT UNDERSTANDS A AMINO ACID ZINC HALOGENIDE COMPLEX AND A CLEANING METHOD OF A TOOTH
    FUNDAMENTALS [001] There is a need for oral care products to whiten teeth. Bleaching materials such as peroxide are commonly used to whiten teeth, but peroxide is difficult to formulate and deliver in sufficient concentrations to provide a good whitening effect. White pigments, such as zinc oxide, are also used, but such insoluble pigments are also difficult to formulate and release.
    [002] There is also a need for improved consumer-friendly products and methods to encourage users to brush their teeth for a long period of time. It is recommended that children should brush their teeth for at least 45 to 60 seconds, and for adults, at least 90 to 120 seconds. Most people, especially children, do not brush their teeth for a period of time long enough to obtain the maximum benefit, and moreover, they have difficulty in accurately estimating the time needed to brush their teeth. Toothpaste comprising fragments of colored or encapsulated films that release pigment upon proper brushing are known, but these pigments do not provide any special benefit to the teeth.
    SUMMARY [003] It is surprisingly discovered that, while the amino acid zinc halide complexes are soluble, colorless and stable in concentrated aqueous solution,
    Petition 870190004015, of 14/01/2019, p. 10/36
    2/23 even at neutral pH, the amino acid zinc halide complex decomposes into a more diluted solution, to provide a relatively insoluble zinc-containing precipitate, for example, a zinc oxide precipitate. This dynamic is surprising because an ionic complex would be expected to remain in solution when the solution becomes more diluted. This precipitation can be useful to signal that a minimum brushing period has elapsed, and, in addition, the precipitation provides for the controlled deposition of the white precipitate containing zinc on the teeth.
    [004] The invention thus provides, in one embodiment, a method for (i) indicating an amount of time for brushing teeth and / or (ii) whitening teeth, which comprises brushing teeth with a toothpaste comprising a complex of amino acid zinc halide, in the presence of water, until the amino acid zinc halide complex provides a zinc precipitate from the toothpaste and water. The method comprises brushing the teeth with a toothpaste containing an amino acid zinc halide complex until the amino acid zinc halide complex decomposes to obtain a white precipitate containing zinc. The time can be, for example, 30 to 120 seconds, for example, 45 to seconds for a child or 90 to 120 seconds for an adult.
    [005] For example, in one embodiment, the toothpaste is a transparent gel. After a period of brushing, for example, at least 30 seconds, the amino acid zinc halide complex is stopped, and the paste
    Petition 870190004015, of 14/01/2019, p. 11/36
    3/23 of transparent gel teeth is suddenly made white and opaque by the precipitate, signaling to the user that he or she has brushed for an appropriate period.
    [006] In a particular embodiment, the amino acid zinc complex is a zinc lysine chloride complex, for example, the new complex called ZLC, which can be formed from a mixture of zinc oxide and lysine hydrochloride . ZLC has the chemical structure [Zn (C6H14N2O2) 2CI] + C1 “, and can exist in cationic cation solution ([[Zn (C6H14N2O2) 2CI] + ) and the chloride anion, or it can be a solid salt, for example, a crystal, optionally in mono- or dihydrate form.
    [007] Other areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and the specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
    DETAILED DESCRIPTION [008] The following description of the preferred embodiment (s) is merely exemplary in nature and is in no way intended to limit the invention, its application or uses.
    [009] The invention thus provides, in particular, embodiments of a method of cleaning and / or whitening teeth (Method 1) which comprises brushing with a dentifrice comprising a zinc amino acid halide complex in the presence of water, until the complex disintegrates, in which the white precipitate thus formed
    Petition 870190004015, of 14/01/2019, p. 12/36
    4/23 provides a signal to the user of proper brushing, and / or provides a whitening benefit to teeth, for example,
    1.1. Method 1 in which the brushing time before the complex disintegrates is between 30 and 180 seconds, for example, about 45 to 60 seconds for a toothpaste for use by a child and about 90 to 120
    seconds for folder of teeth for use per one adult.1.2. Method 1 on what the amino acid in the complex is selected among arginine and lysine, in the form of salt in
    addition of free or orally acceptable acid, for example, hydrochloride form.
    1.3 Any of the preceding methods in which the halide in the complex is selected from chloride, fluoride, bromide and mixtures thereof, for example, chloride.
    1.4. Any of the preceding methods in which in the complex the molar ratio of Zn: amino acid is 3: 1 to 1: 5, for example, about 1: 2 and the molar ratio of Zn: halide is 3: 1 to 1: 3 , for example, about 1: 2
    1.5 Any of the preceding methods, in which zinc is present in an amount of 0.05 to 10% by weight of the toothpaste, optionally at least 0.1, at least 0.2, at least 0.3, at least 0.4 , at least 0.5, at least
    1, at least 2, at least 3, or at least 4 up to 10% in weight of toothpaste, for example, about 1 to 3%, for example, about 2 to 2.7% in weight. 1.6 Any of the methods precedents, on what
    amino acid is present in an amount of 0.05 to 30% by weight of the toothpaste, optionally at least 0.1, at least
    Petition 870190004015, of 14/01/2019, p. 13/36
    5/23 minus 0.2, minus 0.3, minus 0.4, minus 0.5, minus 1, minus 2, minus 3, minus 4, minus 5, minus 10, at least 15, at least 20 to 30% by weight, for example, about 1 to 10% by weight.
    1.7 Any of the preceding methods, in which the dentifrice comprises a molar ratio of zinc to amino acid is 2: 1 to 1: 4, optionally, 1: 1 to 1: 4, 1: 2 to 1: 4, 1: 3 to 1: 4, 2: 1 to 1: 3.2: 1 to 1: 2, or 2: 1 to 1: 1, for example, about 1: 2 or 1: 3
    1.8 Any of the preceding methods in which the amino acid zinc complex is a lysine zinc chloride complex (for example, (ZnLyszCl) + C1 “or (ZnLysa) 2 + Clz) or an arginine zinc chloride complex
    1.9 Any of the preceding methods, in which the amino acid zinc complex is a lysine zinc chloride complex, for example, ZLC, for example, a lysine zinc chloride complex having the chemical structure [Zn (C6H14N2O) 2CI] + C1 “Either in cationic cation solution (for example, [Zn (C6H14N2O2) 2CI] + ) and the chloride anion, or in solid salt form, for example, crystal form, optionally in mono or dihydrate form
    1.10 Any of the preceding methods, in which the toothpaste is in the form of a transparent gel, which provides a zinc oxide precipitate when diluted
    1.11 Any of the preceding methods, in which the halide - amino acid - zinc complex is present in the dentifrice an effective amount, for example, in an amount corresponding to 0.1 to 3% by weight of zinc, for example, about 0, 2 to 1% by weight of zinc in the toothpaste
    1.12 Any of the preceding methods additionally
    Petition 870190004015, of 14/01/2019, p. 14/36
    6/23 providing a benefit of selected oral care to reduce and inhibit acid enamel erosion, cleaning teeth, reducing bacterially generated biofilm and plaque, reducing gingivitis, inhibiting tooth decay and cavity formation, and / or reducing teeth hypersensitivity.
    1.13. Any of the preceding methods, in which the dentifrice is in the form of a transparent gel, in which the halide complex -amino acid-zinc is a complex of lysine-zinc chloride having the chemical structure [Zn (C6H14N2O2) 2CI ] + C1 “present in an amount corresponding to 0.1 to 2%, for example, about 0.5% of zinc by weight of the toothpaste, and which further comprises humectant, for example, sorbitol, propylene glycol and mixtures thereof, for example, in an amount of 45 to 65%, for example, about 50 to 60%, thickeners, for example, cellulose derivatives, for example, selected from carboxymethyl cellulose (CMC), trimethyl cellulose (TMC) and their mixtures, for example, in an amount of 0.1 to 2%, sweetener and / or flavorings, and water, for example, in which the dentifrice is an oral gel comprising:
    Ingredients o_ O Sorbitol 40 to 60%, eg 50 to 55% ZLC to provide 0.1 to 2% Zn, eg about 0.5% Zn Carboxymethyl cellulose (CMC) and trimethyl cellulose (TMC) 0.5% to 1%, eg about0.7% Flavoring and sweetening 0.01 to 1% Propylene glycol 1 to 5%, eg about3.00%
    Petition 870190004015, of 14/01/2019, p. 15/36
    7/23 [0010] The invention also provides for the use of an amino acid zinc halide complex in a method according to any of the preceding methods 1, et seq. or in the manufacture of a toothpaste for use in any of the preceding methods 1, et et seq.
    [0011] The combination of zinc, amino acid, and halide in an aqueous medium forms a cationic halide-complex salt. The amino acid zinc halide is a water-soluble complex formed from the halide acid addition salt (eg, zinc chloride) and an amino acid, or from the halide acid addition salt of an amino acid (eg example, lysine hydrochloride) and source of zinc ions, for example, zinc oxide or TBZC, and / or from a combination of all three of a halogen acid, an amino acid, and a source of zinc ion.
    [0012] The source of zinc ion for the combination with an amino acid hydrohalide or an amino acid plus halogen acid can be any source that provides Zn ++ ions efficiently, for example, zinc oxide, zinc chloride, chloride tetrabasic zinc, zinc carbonate, zinc nitrate, zinc citrate, and zinc phosphate. Zinc oxide is a white powder, insoluble in water. Tetrabasic zinc chloride (TBZC) or hydroxide zinc chloride monohydrate is a zinc hydroxy compound with the formula Zns (OH) eClz · H2O, also referred to as basic zinc chloride, zinc hydroxychloride, or zinc oxychloride. It is a colorless crystalline solid insoluble in water. Both of these materials are found to be water-soluble in the presence of an amino acid and provide a source of ions
    Petition 870190004015, of 14/01/2019, p. 16/36
    8/23 of zinc, while restricting the available anions, as an excess of anions can interfere with the formation of the complex.
    [0013] The source of the amino acid can be any amino acid. Examples of amino acids include, but are not limited to, common natural amino acids, for example: lysine, arginine, histidine, glycine, serine, threonine, asparagine, glutamine, cysteine, selenocysteine, proline, alanine, valine, isoleucine, leucine, methionine, phenylalanine, tyrosine, tryptophan, aspartic acid, and glutamic acid.
    [0014] In some embodiments, the amino acid is a basic amino acid. By basic amino acid means the naturally occurring basic amino acids, such as arginine, lysine and histidine, as well as any basic amino acid having a carboxyl group and an amino group in the molecule, which is soluble in water and provides an aqueous solution with a pH of about 7 or higher. Consequently, basic amino acids include, but are not limited to, arginine, lysine, citrulline, ornithine, creatine, histidine, diaminobutanoic acid, diaminoproprionic acid, their salts or combinations thereof. In certain embodiments, the amino acid is lysine. In other embodiments, the amino acid is arginine. Neutral amino acids, such as glycine, and even acidic amino acids, such as aspartic acid, however, are also capable of forming salts with strong acids, such as halogen acids. In some embodiments, the amino acid is a neutral or acidic amino acid, for example, glycine.
    Petition 870190004015, of 14/01/2019, p. 17/36
    9/23 [0015] The halide source may be part of the zinc source, such as zinc chloride or tetrabasic zinc chloride. The halide source may be part of the amino acid, such as a hydro-halolegent amino acid. In addition, the halide source may be a halogen acid. The halide can be chloride, bromide, or iodide, more typically chloride. Acid addition salt of an amino acid and a halogen acid (for example, HCI, HBr, or HI) is sometimes referred to here as an amino acid hydrohalide. Thus an example of an amino acid hydrohalide is lysine hydrochloride. Another is glycine hydrochloride.
    [0016] In certain embodiments, the amount of amino acid zinc halide in the composition for use in the methods described above is 0.05 to 40% by weight of the composition. In certain embodiments, for example, precursors, zinc oxide and amino acid hydrohalide, are present in amounts such that when combined in the amino acid zinc halide, the amino acid zinc halide would be present in an amount of 0, 05 to 40% by weight of the composition. In both embodiments, the amount of the amino acid zinc halide can be varied for the desired purpose, such as an antibacterial agent or an antiperspirant. In other embodiments, the amino acid zinc halide is present in an amount of 0.05 to 40% by weight of the composition, optionally at least 0.1, at least 0.2, at least 0.3, at least 0 , 4, at least 0.5, at least 1, at least 2, at least 3, or at least 4 to 40% by weight of the composition, or, optionally, 0.1
    Petition 870190004015, of 14/01/2019, p. 18/36
    10/23
    up to 30%, up to 20%, up until 10%, up to 5%, up to 4%, up to 3%, up to 2%, or up to 1% by weight gives composition.[0017] When O zinc halide amino acid is formed to leave in zinc is precursor materials, the materials precursors are preferably used in
    molar ratios approximately as needed to produce the desired amino acid zinc halide, although an excess of one material or another may be desirable, in certain formulations, for example, to balance the pH against other components of the formulation, to provide additional antibacterial zinc, or to provide amino acid buffer. Preferably, however, the amount of the halide is limited, when restricting the level of the halide encourages interaction between zinc and the amino acid. For example, in an embodiment for the production of lysine zinc chloride (ZnLysaClz), the molar ratios of the elements in the precursor materials will include about 1 molar equivalent of Zn 2+ : 3 molar equivalents of Lys: 2 molar equivalents of Cl " .
    [0018] In some embodiments, the total amount of zinc in the toothpaste for use in the present invention is 0.05 to 3% by weight of the toothpaste. In other embodiments, the total amount of zinc is at least 0.1, at least 0.2, at least 0.3, at least 0.4, at least 0.5, or at least 1 through 2 , 5 or 3% by weight of the toothpaste. In other embodiments, the total amount of zinc in the toothpaste is less than 5, less than 4, less than 3, less than 2 or less than 1 to 0.05% by weight of the composition.
    [0019] In certain embodiments, a molar ratio
    Petition 870190004015, of 14/01/2019, p. 19/36
    11/23 of zinc for amino acid in dentifrice for use in the methods of the invention is at least 2: 1. In other embodiments, the molar ratio is at least 1: 1, at least 1: 2, at least 1: 3, at least 1: 4.2: 1 to 1: 4.1: 1 to 1 : 4, 1: 2 to 1: 4, 1: 3 to 1: 4.2: 1 to 1: 3, 2: 1 to 1: 2.2: 1 to 1: 1, or 1: 3. Above 1: 4, it is expected that the zinc will be fully dissolved.
    [0020] In certain embodiments, the amino acid zinc halide is a zinc lysine complex that has the formula [Zn (C6H14N2O2) 2CI] + C1 “(sometimes referred to here as ZLC).
    [0021] In certain embodiments, the amino acid zinc halide has the formula ZnAA3Hal2, where Zn is a divalent zinc ion, AA is an amino acid residue, and Hal represents a halide ion.
    [0022] Some embodiments of the present invention provide methods for cleaning a tooth comprising: administering a composition comprising a zinc halide complex amino acid in the oral cavity; and retaining the composition in the oral cavity for a time sufficient to form a precipitate. In some embodiments, the precipitate provides a signal to the user. In some embodiments, the signal is a visually perceptible signal. In some embodiments, the sign indicates that the composition has been used for the appropriate time.
    [0023] In some embodiments, the composition forms a precipitate after 30 seconds in the oral cavity. In some embodiments, the composition forms a precipitate after 90 seconds in the oral cavity. In some
    Petition 870190004015, of 14/01/2019, p. 20/36
    12/23 embodiments, the composition forms a precipitate after 120 seconds in the oral cavity.
    [0024] Compositions and formulations for use with the methods described herein with reference to their ingredients, as is customary in the art. As would be apparent to a person skilled in the art, the ingredients may in some cases react with each other, so that the actual composition of the final formulation may not correspond exactly to the listed ingredients. Thus, it should be understood that the invention extends to the product of the combination of the listed ingredients.
    [0025] As used throughout, ranges are used as an abbreviation to describe each value that is within the range. Any value within the range can be selected as the end of the range. In addition, all references cited herein are hereby incorporated by reference in their entirety. In the event of a conflict in a definition in this disclosure and that of a cited reference, these disclosure controls.
    [0026] Unless otherwise stated, all percentages and quantities here and elsewhere expressed in the specification should be understood as referring to percentages by weight. The quantities given are based on the active weight of the material.
    EXAMPLES
    Example 1 [0027] The general reaction for the formation of ZLC is as follows:
    ZnO + 2 (Lysine-HCI) -> [Zn (Lysine) 2 C1] Cl-2H 2 O (ZLC)
    A molar ratio of 2: 1 suspension of ZnO: Lysine-HCI is
    Petition 870190004015, of 14/01/2019, p. 21/36
    13/23 prepared with stirring at room temperature for about 12 hours. The mixture is centrifuged. 1 ml of the supernatant is transferred to an NMR tube. The NMR tube is then placed in a closed test tube, filled with ethanol during the growth of the crystal. A number of colorless cubic crystals are formed after one week. The crystal structure of the ZLC crystal is determined by single crystal X-ray diffraction. The fundamental parameters for this structure are: Crystal System: Monoclinic, Space group: P21: Cell dimensions of the unit: a = 5.2751 (8) Â, b = 17.055 (3) Â, c = 11.4072 (18) THE. α = 90 °, β = 94.064 (2) °, γ = 90 °. In this complex, the Zn cation is coordinated by two lysine ligands with two N atoms of the NH2 groups and O atoms of the carboxylic groups in an equatorial plane. It exhibits a distorted square pyramid geometry with the apical position occupied by a Cl atom. This new structure gives rise to a portion of positive cation, for which a Cl anion is combined to form an ionic salt.
    [0028] Laboratory scale-up synthesis of pure ZLC powder: 2 moles of LisinaHCl are dissolved in 1000 ml of Dl water, with stirring at room temperature, 1 mole of solid ZnO is added slowly to the LisinaHCl solution with stirring and stirring is continued overnight at RT (about 12 hours). The suspension solution is centrifuged at high speed for 15 min. The supernatant is slowly poured into EtOH. A precipitate is formed immediately. Approximately 5 to 8 ml of EtOH is required to obtain 1 g of the powder. The powdered EtOH solvent is filtered, and an off-white powder is obtained. The powder is placed in an oven at
    Petition 870190004015, of 14/01/2019, p. 22/36
    14/23 ° C during drying and a yield of 88% of the product is obtained. PXRD confirms the purity of the ZLC powder compared to ZLC crystal.
    Example 2 [0029] An oral gel toothpaste with ZLC as an active ingredient is formulated and compared with other formulations containing ZnClz, ZnO, and NaF. Only the ZLC formulation shows competitive clarity as a real gel phase containing NaF. The ZLC gel phase precipitation property is also investigated by the hydrolysis reaction study, providing evidence that when teeth are being brushed with toothpaste containing ZLC assets, insoluble particles formed during brushing can penetrate the tubules teeth and block the tubules resulting in anti-sensitive effect and signal to the consumer.
    [0030] Four gel phase lots containing 500, NaF Og (control), ZLC, ZnClz and ZnO as an active ingredient are formulated with the ingredients shown in Table 1. The clarity of the samples with different active ingredients is compared, and the precipitation characteristic of the ZLC gel phase by dilution is evaluated. The concentration of zinc ions in ZLC solution is 25300 ppm obtained by ICP, which in terms of weight gives about 17% of ZLC assets in the solution. Concentration of zinc ions in the following batches are all prepared at a zinc level of 0.5% (w / w).
    Table 1
    Oral gel with ZLC (2.53% Zn)Ingredients o_ “O Load (g) Real(g)
    Petition 870190004015, of 14/01/2019, p. 23/36
    15/23
    Sorbitol 70% sun. 76, 03 380.15 380.142.53% ZLC aqueous solutionfrom Zn 20 100 100Carboxymethyl cellulose (CMC), trimethyl cellulose (TMC) 0.70 3.5 3.51Na saccharin 0.27 1.35 1.35Propylene glycol 3 15 15Total 100 500 500% of Zn 0.5060.5060%
    Oral gel with ZnClz (47.97% Zn)Ingredients o_ O Load (g) Actual (g)Sorbitol 70% sun. 80 400 399.99ZnClz 47.97% Zn 1.06 5.275 5.27CMC TMC 0.7 3.5 3.5Na saccharin 0.27 1.35 1.35Propylene glycol 3 15 14.98DI water 14.98 74,875 74.91Total 100 500 500% of Zn 0.5080.5056%
    Oral gel with ZnO (80.34% Zn)Ingredients o_ O Load (g) Actual (g)Sorbitol 70% sun. 80.2 401 400.99ZnO 80.34% Zn 0.63 3.15 3.15CMC TMC 0.7 3.5 3, 5Na saccharin 0.27 1.35 1.35
    Petition 870190004015, of 14/01/2019, p. 24/36
    16/23
    Propylene glycol 3 15 15DI water 15.2 76 75.99Total 100 500 499.98% of Zn 0.5500.5062%
    Oral gel with NaFIngredients o_ “O Load (g) Actual (g)Sorbitol 70% sun. 80.20 401 401In F 0.76 3, 8 3.79CMC TMC 0.7 3.5 3, 51Na saccharin 0.27 1.35 1.35Propylene glycol 3 15 15, 01DI water 15, 07 75.35 75.36Total 100 500 500.02
    [0031] Lambda 25 UV / VIS spectrometer (Perkin Elmer) is used to obtain absorbance information for all samples, in order to compare the clarity of the gel phase between the different assets. Absorbance is a logarithmic measure of the amount of light that is absorbed when it passes through a substance. Once the particles of the gel absorb light, the more particles in the solution, the more luminous absorbed by the gel. Thus, a small number of absorbances of a gel indicates greater clarity. The absorbance is corrected using deionized water (DI) as the blank solution under the 610nm wavelength light source. ZnO is not dissolved and is suspended in a gel phase resulting in a high absorbance. Although ZnClz is water-soluble, the gel phase that contains
    Petition 870190004015, of 14/01/2019, p. 25/36
    17/23
    ZnClz appears cloudy. Only the gel phase formulated by ZLC forms a homogeneous solution and shows competitive clarity as the gel phase formulated by NaF. The absorbance and pH of all samples are shown in Table 2.
    Table 2
    In F ZLC Zn Cl 2 ZnO Absorbance 0.0344 0.1765 0.9204 2.4626 PH 7.63 7.37 5, 25 8.30
    [0032] Dilution experiment: All original gel phase batches are diluted 2 times, 4 times, 8 times, 16 times and 32 times. There is a decrease in absorbance as the ZnClz gel and ZnO gel are more diluted, and an increase in absorbance in the additional diluted ZLC gel solution. This observation confirms the formation of a precipitate when ZLC gel is being diluted with water. At pH values of 2 times, 4 times, 8 times, 16 times, 32 times diluted the ZLC gel solution is 7.71, 7.91, 8.03, 8.12, and 8.14, respectively.
    Table 3
    Ingredientactive 2-fold dilution 4-fold dilution 8-fold dilution 16-fold dilution Dilutionof 32times In F 0.0106 0.0104 0.0107 0.0075 0.0137 ZLC 0.1436 0.1887 0.1860 0.1336 0.2998 ZnCl 2 0.7315 0.3700 0.1701 0.0570 0.0280 ZnO 2.4630 2.5340 2.1883 1.8638 1.0492
    [0033] The gels above can be used alone (preferred where the purpose is to provide a signal to the user of the proper brushing time) or in a toothpaste that has a gel phase and a paste phase
    Petition 870190004015, of 14/01/2019, p. 26/36
    18/23
    abrasive. ZLC how ingredient active in phase of gel in formulation in folder of teeth. Compared with the lots in phase of gel formulated by ZnClz and ZnO, only The
    formulation with ZLC as an active shows competitive clarity and pH as one used in the commercial product (NaF as active ingredient). The dilution experiment shows that the single ZLC gel phase can form insoluble precipitate of transparent gel when it is diluted. The formation of an insoluble precipitate by dilution facilitates the formation of plugs in dentin tubules after using this type of toothpaste, which whitens the teeth, and which provides
    a white precipitate sign while using the user. Example 3 [0034] Various dilutions in ZLC are prepared for evaluate the your efficiency at production of precipitates
    visible and / or flocculation, which can be distributed on a tooth surface (dentin and / or enamel) for whitening benefits.
    [0035] A pure ZLC solution is prepared by 1), reacting 0.5 mol of ZnO powder with 1 mol of lysine HC1 in 1 liter of water at room temperature for about 2 hours, and 2) collecting the supernatant by means of centrifugation followed by filtration through a 0.45 micron membrane. The pure solution has a zinc concentration of 2.39% by weight, and a pH of about 7.03.
    [0036] Dilution experiment is conducted by mixing the pure solution with deionized water. The pure solution is diluted by 2x, 4x, 6x, 7x, 8x, 10x, 12x, 16x, 20x, 24x, 28x, and 32x, corresponding to initial concentrations of
    Petition 870190004015, of 14/01/2019, p. 27/36
    19/23 1.20% zinc, 0.598%, 0.398%, 0.341%, 0.299%, 0.239%, 0.199%, 0.149%, 0.120%, 0.0996%, 0.0854%, 0.0747%, in weight, respectively. The diluted samples are kept at 37 ° C, and the rates at which flocculation / precipitation occurred are monitored. Dilutions with initial concentrations of zinc at 0.149% and 0.199% are capable of generating some visible flocculation within 30 minutes from the time point when the stock solution is mixed with water. One hour of mixing, visible flocculation is observed in dilutions with initial zinc concentrations between 0.0854% and 0.239%. One and a half hours after mixing, visible flocculation is observed in dilutions with initial zinc concentrations between 0.0747% and 0.239%. Two hours after mixing, the additional sample with the initial zinc concentration of 0.299% also showed the presence of flocculation. After a total of 19 hours, flocculation and / or precipitation can be observed in all samples except the one with an initial zinc concentration of 1.20%, and those with an initial zinc concentration of between 0.0747% and 0.239%, exhibit the majority of precipitates.
    [0037] The pH values of the diluted final samples are suitable for oral care applications. Samples with initial zinc concentrations of 0.0747%, 0.0854%, 0.0996%, 0.120%, 0.149%, 0.199% and 0.239% had a final pH value of 7.99, 8.13, 8 , 11, 7.97, 7.99, 6, 80, and 6.70, respectively. These pH values are well within the range of 5.5 to 10, which defines the appropriate range for oral care formulations.
    [0038] Zinc is present in the precipitates mainly in the form of zinc oxide. Lysine is
    Petition 870190004015, of 14/01/2019, p. 28/36
    20/23 present in the precipitate as an integral component of it and / or as an impurity.
    Example 4 [0039] Confocal images demonstrate the efficiency of ZLC in generating deposits on the dentin surface, under conditions in which visible precipitation can be formed. The deposits give a white color to the dentin surface, after examination by the naked eyes.
    [0040] The deposition / occlusion test is conducted using slices of human dentin and the pure solution of Example 3. Dentin slices are prepared by cutting human tooth into thin dentin sections about 800 microns thick, which designates a test side, sand said test side using sanding paper of about 600 sand, polishing said test side using a Buehler polishing cloth and 5 micron Buehler aluminum oxide, acid etching that section dentin in 1% (by weight) of citric acid solution for about 20 seconds, sonicating said dentin section for 10 minutes, and storing said dentin section in phosphate buffered saline (PBS, pH 7, 4, Gibco Cat. No. 10010).
    [0041] For the treatment, the pure solution is diluted 16 times with water, obtaining a treatment solution with an initial zinc concentration of about 0.149% by weight. The dentin section is immersed in the treatment solution for 1 hour at 37 ° C. The treated dentin section is then removed from the treatment solution, and washed 4 times, each time with 1 ml of PBS. The dentin section is then dried using a paper-based tissue and examined under
    Petition 870190004015, of 14/01/2019, p. 29/36
    21/23 confocal microscope in both XYZ and XYZ modes. Subsequent treatments are carried out in the same way.
    [0042] Progressive deposition and occlusion can be seen through confocal imaging. The first treatment leads to noticeable deposition. The second treatment leads to complete coverage of the surface, including blocking substantially all of the tubule openings. Surface deposits can be 10 microns or more in thickness. After the third treatment, complete coverage of the surface and complete blockage of tubule openings are observed. The surface deposits can be 25 microns or more in thickness.
    Example 5 [0043] Confocal images demonstrate the efficiency of the ZLC in generating deposition on the dentin surface, under conditions where visible precipitation is not observed.
    [0044] A new section of dentin, as prepared following the procedure of Example 4, is treated repeatedly with dilutions of ZLC with the initial zinc concentration of 0.0747% by weight. Each treatment involved 32 ml of diluted solution (1 ml of a pure solution of Example 3 and 31 ml of deionized water) and last for 10 minutes at 37 ° C, during which time no precipitation is observed by the naked eye . The dentin section is examined under the confocal microscope after each treatment. After 4 consecutive treatments, significant surface deposition is observed. After 12 consecutive treatments, the complete surface coverage is observed, leaving no sign of the presence of openings in the tubule.
    Petition 870190004015, of 14/01/2019, p. 30/36
    22/23 [0045] Therefore, deposition on the surface can occur under conditions, either in terms of dilution ratios and treatment durations that do not produce visible precipitation. As a result, the bleaching benefits can be achieved over broader ranges of dilution ratios and shorter treatment times than what can be directly inferred from examples 3 and 4.
    Example 6 [0046] Spectrophotometric analysis proves the efficacy of bleaching treatment with ZLC. After the third treatment, the dentin section of Example 4 is dried and examined under a Spectroshade ™ spectrophotometer (Handy dental Type 71.3000). The treated area of dentin is included and the enamel ring is excluded from subsequent examination and data processing. The CIELAB color reading is L * = 86.6, a * = -1.7, and b * = 1.5. A similarly prepared section of dentin without treatment produced a reading of L * = 12.5, a * = - 1, 9, and b * = 10.3. It is generally understood that, by definition, L * = 0 means black and L * = 100 indicates diffuse white, negative a * value indicates green, while positive values indicate magenta, and negative h * values indicate blue and positive values indicate yellow. It can be concluded that treatment with ZLC improved the total whiteness and reduced the yellowing of the dentin surface.
    [0047] Although the invention has been described with respect to specific examples including presently preferred ways of carrying out the invention, those skilled in the art will appreciate that there are numerous variations and permutations of the systems and techniques described above. Is for
    Petition 870190004015, of 14/01/2019, p. 31/36
    It will be understood that other embodiments can be used and structural and functional modifications can be made without departing from the scope of the present invention. Thus, the scope of the invention should be interpreted widely as set out in the appended claims.
    权利要求:
    Claims (11)
    [1]
    1. Use of an amino acid zinc halide complex characterized by the fact that it is in the preparation of a tooth cleaning composition.
    [2]
    2. Composition comprising a zinc halide amino acid complex, characterized by the fact that when the composition is retained in the oral cavity between 30 and 180 seconds to form a precipitate, the precipitate provides a signal to the user, and in which the amino acid is selected from lysine and arginine.
    [3]
    Composition according to claim 2, characterized by the fact that the amino acid zinc halide complex is a lysine zinc chloride complex or an arginine zinc chloride complex.
    [4]
    4. Method of cleaning a tooth characterized by the fact that it comprises:
    administering a composition comprising an amino acid zinc halide complex, in an amount of 0.1 to 3% by weight of zinc in the composition, in the oral cavity; and retain the composition in the oral cavity for 30 to 180 seconds to form a precipitate, in which the amino acid is selected from lysine and arginine, and in which the composition is in the form of a clear gel that provides a precipitate of oxide of zinc when diluted.
    [5]
    5. Method according to claim 4, characterized by the fact that the precipitate provides a signal to the user.
    [6]
    6. Method according to claim 5,
    Petition 870190042693, of 05/06/2019, p. 8/10
    2/3
    featured by the fact that the sign is a signal visually noticeable. 7. Method, according with the claim 5 or 6, featured by the fact that the sign indicates that composition was used during appropriate time.
    [7]
    Method according to any one of claims 4 to 7, characterized in that the composition is diluted to a sufficient degree to form a precipitate after 30 seconds in the oral cavity.
    [8]
    Method according to any one of claims 4 to 8, characterized in that the composition is diluted to a sufficient degree to form a precipitate after 90 seconds in the oral cavity.
    [9]
    Method according to any one of claims 4 to 9, characterized in that the composition is diluted to a sufficient degree to form a precipitate after 120 seconds in the oral cavity.
    [10]
    Method according to any one of claims 4 to 10, characterized in that the precipitate is a white precipitate and in which the precipitate provides a whitening benefit to the teeth.
    12. Method, in a deal with any an of claims 4 to 11, featured by the fact in that the amino acid zinc halide complex is a complex of zinc chloride lysine or a complex chloride in zinc arginine. 13. Method, in a deal with any an of claims 4 to 12, featured by the fact in that the
    amino acid zinc halide complex is a lysine zinc chloride complex that has the chemical structure
    Petition 870190042693, of 05/06/2019, p. 9/10
    3/3 [Zn (C 6 H 14 N 2 O2) 2 C1] + C1-.
    [11]
    Method according to any one of claims 4 to 13, characterized in that the composition is in the form of a transparent gel which provides a zinc oxide precipitate when diluted.
    类似技术:
    公开号 | 公开日 | 专利标题
    US11197811B2|2021-12-14|Teeth whitening methods, visually perceptible signals and compositions therefor
    US10588841B2|2020-03-17|Oral care compositions comprising zinc amino acid halides
    US10524995B2|2020-01-07|Zinc amino acid halide mouthwashes
    AU2012397265B2|2016-02-25|Oral gel comprising zinc - amino acid complex
    BR112015014253B1|2019-04-09|Oral care composition comprising a tetrabasic and amino acid zinc halide complex and uses of the complex
    同族专利:
    公开号 | 公开日
    AU2012397269B2|2015-10-29|
    AR094207A1|2015-07-15|
    EP2934445A1|2015-10-28|
    TW201436814A|2014-10-01|
    MX353167B|2017-12-20|
    MX2015007786A|2015-08-20|
    US20150335552A1|2015-11-26|
    US11197811B2|2021-12-14|
    BR112015014444A2|2017-07-11|
    CN104853728A|2015-08-19|
    US20200206115A1|2020-07-02|
    US20180256468A1|2018-09-13|
    TWI522122B|2016-02-21|
    US10610475B2|2020-04-07|
    AU2012397269A1|2015-06-18|
    US20170128339A1|2017-05-11|
    US9993407B2|2018-06-12|
    WO2014098828A1|2014-06-26|
    CN104853728B|2018-07-24|
    EP2934445B1|2017-10-04|
    US9572756B2|2017-02-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE735096C|1940-12-09|1943-05-06|Ig Farbenindustrie Ag|Process for the production of sulphonic acids|
    US2527686A|1945-12-26|1950-10-31|Max H Sandberg|Mouthwash|
    US2503280A|1947-10-24|1950-04-11|Du Pont|Azo catalysts in preparation of sulfonic acids|
    US2507088A|1948-01-08|1950-05-09|Du Pont|Sulfoxidation process|
    US2893918A|1957-04-24|1959-07-07|Harold A Abramson|Deodorant composition|
    FR1247957A|1958-09-28|1960-12-09|Ajinomoto Kk|Process for the continuous separation of racemic amino acids|
    US3320174A|1964-04-20|1967-05-16|Colgate Palmolive Co|Detergent composition|
    US3372188A|1965-03-12|1968-03-05|Union Oil Co|Sulfoxidation process in the presence of sulfur trioxide|
    US3538230A|1966-12-05|1970-11-03|Lever Brothers Ltd|Oral compositions containing silica xerogels as cleaning and polishing agents|
    US3678154A|1968-07-01|1972-07-18|Procter & Gamble|Oral compositions for calculus retardation|
    US3535421A|1968-07-11|1970-10-20|Procter & Gamble|Oral compositions for calculus retardation|
    US3741911A|1970-12-21|1973-06-26|Hart Chemical Ltd|Phosphate-free detergent composition|
    US3959458A|1973-02-09|1976-05-25|The Procter & Gamble Company|Oral compositions for calculus retardation|
    US3937807A|1973-03-06|1976-02-10|The Procter & Gamble Company|Oral compositions for plaque, caries, and calculus retardation with reduced staining tendencies|
    US3862307A|1973-04-09|1975-01-21|Procter & Gamble|Dentifrices containing a cationic therapeutic agent and improved silica abrasive|
    US3941818A|1973-08-20|1976-03-02|Zinpro Corporation|1:1 Zinc methionine complexes|
    US4021569A|1973-08-20|1977-05-03|Zinpro Corporation|Method of nutritional supplementation for zinc and methionine by ingesting 1:1 zinc methionine complexes|
    US4051234A|1975-06-06|1977-09-27|The Procter & Gamble Company|Oral compositions for plaque, caries, and calculus retardation with reduced staining tendencies|
    US4021459A|1975-08-14|1977-05-03|Schering Corporation|Process for the preparation of 21-halogeno-21-desoxy-17α-acyloxy 20-keto-pregnenes|
    US4340583A|1979-05-23|1982-07-20|J. M. Huber Corporation|High fluoride compatibility dentifrice abrasives and compositions|
    GB2052978A|1979-06-20|1981-02-04|Unilever Ltd|Oral compositions containing zinc salts|
    US4339432A|1979-06-20|1982-07-13|Lever Brothers Company|Oral mouthwash containing zinc and glycine|
    US4316824A|1980-06-26|1982-02-23|The Procter & Gamble Company|Liquid detergent composition containing alkyl sulfate and alkyl ethoxylated sulfate|
    JPS57158724A|1981-03-26|1982-09-30|Shiseido Co Ltd|Antimicrobial composition|
    US4565693A|1981-11-09|1986-01-21|Colgate-Palmolive Company|Deodorant composition|
    US4487757A|1981-12-28|1984-12-11|Colgate-Palmolive Company|Dispensing container of toothpaste which effervesces during toothbrushing|
    IL64700D0|1982-01-01|1982-03-31|Binderman Itzhak|Dental care compositions|
    US4885155A|1982-06-22|1989-12-05|The Procter & Gamble Company|Anticalculus compositions using pyrophosphate salt|
    DE3238118C2|1982-10-14|1988-07-28|Verla-Pharm, Arzneimittelfabrik Apotheker H.J. V. Ehrlich Gmbh & Co Kg, 8132 Tutzing, De|
    US4687663B1|1983-03-01|1997-10-07|Chesebrough Ponds Usa Co|Dental preparation article and method for storage and delivery thereof|
    CA1243952A|1984-06-11|1988-11-01|John C. Godfrey|Flavor of zinc supplements for oral use|
    US4599152A|1985-05-24|1986-07-08|Albion Laboratories|Pure amino acid chelates|
    US5188821A|1987-01-30|1993-02-23|Colgate-Palmolive Company|Antibacterial antiplaque oral composition mouthwash or liquid dentifrice|
    US5192531A|1988-12-29|1993-03-09|Colgate-Palmolive Company|Antibacterial antiplaque oral composition|
    US4866161A|1987-08-24|1989-09-12|University Of South Alabama|Inhibition of tartar deposition by polyanionic/hydrophobic peptides and derivatives thereof which have a clustered block copolymer structure|
    US5004597A|1987-09-14|1991-04-02|The Procter & Gamble Company|Oral compositions comprising stannous flouride and stannous gluconate|
    US4842847A|1987-12-21|1989-06-27|The B. F. Goodrich Company|Dental calculus inhibiting compositions|
    US5061815A|1988-07-06|1991-10-29|Zinpro Corporation|Metal lysine complexes and method for producing metal lysine complexes|
    US5156845A|1990-05-04|1992-10-20|Colgate-Palmolive Company|Dry mouth lozenge|
    GB2243775A|1990-05-09|1991-11-13|Unilever Plc|Oral compositions|
    JPH0578243A|1990-12-11|1993-03-30|Shiseido Co Ltd|Antipruritic agent and antipruritic composition|
    GB9107833D0|1991-04-12|1991-05-29|Unilever Plc|Treatment of periodontitis|
    US5643559A|1991-10-30|1997-07-01|Colgate-Palmolive Company|Deodorant compositions comprising inhibitors of odor-producing axillary bacterial exoenzymes|
    US5330748A|1993-05-19|1994-07-19|Church & Dwight Co., Inc.|Dentifrices containing zinc oxide particles|
    US5504055A|1994-03-15|1996-04-02|J.H. Biotech, Inc.|Metal amino acid chelate|
    US5707679A|1994-09-30|1998-01-13|Kemin Industries, Inc.|Metal propionates for use as animal feed supplements|
    EP1203575B1|1995-05-03|2010-09-01|Unilever N.V.|Clear gel-type dentrifices|
    US5714447A|1996-01-24|1998-02-03|Church & Dwight Co., Inc.|Deodorant soap or detergent composition containing a zinc compound and a polyamine|
    US5698724A|1996-04-30|1997-12-16|Zinpro Corporation|Amino acid metal complexes using hydrolyzed protein as the amino acid source and methods re same|
    AU4428397A|1996-09-20|1998-04-14|Warner-Lambert Company|Oral compositions containing a zinc compound|
    GB9622659D0|1996-10-31|1997-01-08|Unilever Plc|Hair treatment composition|
    US5897891A|1996-11-18|1999-04-27|Godfrey; John C.|Flavorful zinc compositions for oral use incorporating copper|
    FI106923B|1997-01-03|2001-05-15|Cultor Ltd Finnsugar Bioproduc|Use of trimethylglycine in preparations for hygiene and care of the mucous membranes of the body|
    US5993784A|1997-07-24|1999-11-30|Whitehill Oral Technologies|Low foaming therapeutic toothpastes with improved cleaning and abrasion performance|
    DK176196B1|1997-10-07|2007-01-08|Ejvind Jersie Pedersen|Oral hygiene composition for the treatment of halitosis and the use of a chelate comprising a metal ion moiety and an amino acid moiety as a component of the composition|
    IL140095A|1998-06-09|2005-11-20|Embro William J|Composition for the treatment of epidermal irritations and infections|
    US6558710B1|1999-06-14|2003-05-06|Helen Rebecca Godfrey|Topical zinc compositions and methods of use|
    US6685920B2|1999-11-12|2004-02-03|The Procter & Gamble Company|Method of protecting teeth against erosion|
    US7164035B2|2000-01-07|2007-01-16|Newsome David A|Zinc-monocysteine complex and method of using zinc-cysteine complexes|
    JP3490950B2|2000-03-15|2004-01-26|三洋電機株式会社|2-cylinder 2-stage compression type rotary compressor|
    DE10160933B4|2001-12-12|2018-06-21|Evonik Degussa Gmbh|Deodorizing compositions containing the zinc salt of ricinoleic acid and at least one amino-functional amino acid|
    US6670494B1|2001-12-17|2003-12-30|J H Brotech, Inc.|Method for preparation of metal organic acid chelates|
    US20040033916A1|2002-06-28|2004-02-19|Kuzmin Vladimir Semenovich|Disinfecting composition|
    JP2004175790A|2002-11-12|2004-06-24|Arita Junichi|ZINC-CONTAINING MATERIAL HAVING alpha-GLUCOSIDASE INHIBITORY EFFECT|
    US7022351B2|2003-01-14|2006-04-04|Zinpro Corporation|Composition for supplementing animals with solutions of essential metal amino acid complexes|
    US20040198998A1|2003-04-04|2004-10-07|Marian Holerca|Glycine-free antiperspirant salts with betaine for enhanced cosmetic products|
    US7270806B2|2004-07-27|2007-09-18|Coty S.A.|Liquid stick antiperspirant|
    US7700079B2|2005-09-26|2010-04-20|Jamie Collins Doss|Therapeutic soap product with UV protection|
    BRPI0619389A2|2005-11-29|2011-10-04|Procter & Gamble|dentifrice composition comprising a binder system comprising hydrophilic clay material|
    CN100366539C|2006-05-25|2008-02-06|黄逸强|Method for preparing microelement additive basic zinc chloride|
    DE102006040302A1|2006-08-29|2008-03-20|Henkel Kgaa|Antiperspirant and deodorant compositions with improved care properties|
    PL1935395T3|2006-12-20|2013-11-29|Unilever Nv|Oral composition|
    US8247398B2|2007-02-17|2012-08-21|Ssv Therapeutics, Inc.|Zinc complexes of natural amino acids for treating elevated copper caused toxicities|
    JP2009084201A|2007-09-28|2009-04-23|Riken Koryo Kogyo Kk|Deodorization treating agent for permanent waving agent and permanent waving agent comprising the same|
    EP2052978B1|2007-10-26|2012-08-15|MultiTec GmbH & Co. KG|Display device with data acquisition device and corresponding method|
    CN101938978A|2008-02-08|2011-01-05|高露洁-棕榄公司|Oral care product and methods of use and manufacture thereof|
    JP2011519969A|2008-05-12|2011-07-14|タグラバイオテクノロジーズリミテッド|Composition for topical application comprising a microencapsulated colorant|
    US20100021573A1|2008-07-22|2010-01-28|Michael J Gonzalez|Compositions and methods for the prevention of cardiovascular disease|
    JP2010132639A|2008-11-10|2010-06-17|Nikko Chemical Co Ltd|Dna damage inhibitor and matrix metalloprotease-1 production inhibitor|
    KR101595033B1|2009-06-24|2016-02-17|챨스 엔.에스. 소파카|Zinc supplementation to increase responsiveness to metalloprotease therapy|
    CN101606639B|2009-07-20|2012-07-25|曹江山|Nursery pig concentrated feed|
    AU2009353312B2|2009-09-30|2013-04-04|Colgate-Palmolive Company|Antiperspirant/deodorant composition|
    MY159488A|2009-10-29|2017-01-13|Colgate Palmolive Co|Dentifrice comprising stannous fluoride plus zinc citrate and low levels of water|
    TWI458497B|2010-01-13|2014-11-01|Colgate Palmolive Co|Stabilization of zinc oxide film in oral compositions|
    BR112012022935A2|2010-03-31|2021-06-01|Colgate-Palmolive Company|oral hygiene composition.|
    CN103156073B|2011-12-13|2015-02-18|北京东方联鸣科技发展有限公司|Nutritional supplement for postpartum dairy cows|
    CN103535536A|2012-07-15|2014-01-29|新沂市佳威饲料有限公司|Method for preparing lactating sow feed|
    CN104853812B|2012-12-19|2018-07-10|高露洁-棕榄公司|Antiperspirant products with protein and hidroschesis salt|
    WO2014098813A1|2012-12-19|2014-06-26|Colgate-Palmolive Company|Zinc amino acid/trimethylglycine halide|
    CN104853726B|2012-12-19|2017-10-24|高露洁-棕榄公司|Include the oral care product of four basic zinc amino acid halide complex|
    CA2892179C|2012-12-19|2020-03-31|Colgate-Palmolive Company|Composition with zinc amino acid/trimethylglycine halide precursors|
    US10494589B2|2012-12-19|2019-12-03|Colgate-Palmolive Company|Method for indicating time for washing or indicating delivery of antibacterial agent|
    KR20150097562A|2012-12-19|2015-08-26|콜게이트-파아므올리브캄파니|Two component compositions containing zinc amino acid halide complexes and cysteine|
    MX352558B|2012-12-19|2017-11-29|Colgate Palmolive Co|Oral care compositions comprising zinc amino acid halides.|
    RU2648513C2|2012-12-19|2018-03-26|Колгейт-Палмолив Компани|Zinc amino acid halide mouthwash|
    US9901523B2|2012-12-19|2018-02-27|Colgate-Palmolive Company|Oral care products comprising zinc oxide and trimethylglycine|
    US9757316B2|2012-12-19|2017-09-12|Colgate-Palmolive Company|Zinc-lysine complex|
    WO2014098821A1|2012-12-19|2014-06-26|Colgate-Palmolive Company|Method for indicating time for washing or indicating delivery of antibacterial agent|
    MX353167B|2012-12-19|2017-12-20|Colgate Palmolive Co|Teeth whitening methods, visually perceptible signals and compositions therefor|comprising zinc amino acid halides.|
    KR20150094651A|2012-12-19|2015-08-19|콜게이트-파아므올리브캄파니|Oral gel comprising zinc - amino acid complex|
    WO2014204439A1|2013-06-18|2014-12-24|Colgate-Palmolive Company|Zinc amino acid halide complex with cysteine|
    US10130571B2|2014-06-18|2018-11-20|Colgate-Palmolive Company|Dentifrice Comprising Zinc-Amino Acid Complex and Phosphates|
    EP3377026B1|2015-12-22|2022-02-02|Colgate-Palmolive Company|Oral care compositions comprising zinc amino acid halides|RU2648513C2|2012-12-19|2018-03-26|Колгейт-Палмолив Компани|Zinc amino acid halide mouthwash|
    WO2014098813A1|2012-12-19|2014-06-26|Colgate-Palmolive Company|Zinc amino acid/trimethylglycine halide|
    US9504858B2|2012-12-19|2016-11-29|Colgate-Palmolive Company|Zinc amino acid halide complex with cysteine|
    MX353167B|2012-12-19|2017-12-20|Colgate Palmolive Co|Teeth whitening methods, visually perceptible signals and compositions therefor|comprising zinc amino acid halides.|
    US10188112B2|2012-12-19|2019-01-29|Colgate-Palmolive Company|Personal cleansing compositions containing zinc amino acid/trimethylglycine halide|
    KR20150094651A|2012-12-19|2015-08-19|콜게이트-파아므올리브캄파니|Oral gel comprising zinc - amino acid complex|
    CN104853812B|2012-12-19|2018-07-10|高露洁-棕榄公司|Antiperspirant products with protein and hidroschesis salt|
    MX352558B|2012-12-19|2017-11-29|Colgate Palmolive Co|Oral care compositions comprising zinc amino acid halides.|
    CN104853726B|2012-12-19|2017-10-24|高露洁-棕榄公司|Include the oral care product of four basic zinc amino acid halide complex|
    US9498421B2|2012-12-19|2016-11-22|Colgate-Palmolive Company|Two component compositions containing tetrabasic zinc-amino acid halide complexes and cysteine|
    US9757316B2|2012-12-19|2017-09-12|Colgate-Palmolive Company|Zinc-lysine complex|
    US9750670B2|2012-12-19|2017-09-05|Colgate-Palmolive Company|Zinc amino acid complex with cysteine|
    AU2012397268B2|2012-12-19|2015-09-24|Colgate-Palmolive Company|Oral care products comprising tetrabasic zinc chloride and trimethylglycine|
    CA2892179C|2012-12-19|2020-03-31|Colgate-Palmolive Company|Composition with zinc amino acid/trimethylglycine halide precursors|
    US9901523B2|2012-12-19|2018-02-27|Colgate-Palmolive Company|Oral care products comprising zinc oxide and trimethylglycine|
    US9675823B2|2012-12-19|2017-06-13|Colgate-Palmolive Company|Two component compositions containing zinc amino acid halide complexes and cysteine|
    US10130571B2|2014-06-18|2018-11-20|Colgate-Palmolive Company|Dentifrice Comprising Zinc-Amino Acid Complex and Phosphates|
    WO2015195118A1|2014-06-18|2015-12-23|Colgate-Palmolive Company|Synthesis of zinc-lysine complex from zinc chloride|
    EP3157934B1|2014-06-18|2018-10-17|Colgate-Palmolive Company|Low ph synthesis of zinc-lysine complex|
    MX368518B|2014-08-08|2019-10-07|Colgate Palmolive Co|Dental stain removal and prevention.|
    MX366144B|2014-10-23|2019-06-28|Colgate Palmolive Co|Oral care compositions comprising zinc compounds and peroxide compounds.|
    CN111432784A|2017-12-13|2020-07-17|高露洁-棕榄公司|Dentifrice comprising zinc-amino acid complex|
    US11091502B2|2018-12-21|2021-08-17|Colgate-Palmolive Company|Methods for synthesizing zinc-lysine-chloride complex|
    US11229591B2|2018-12-21|2022-01-25|Colgate-Palmolive Company|Methods for synthesizing zinc-lysine-chloride complex|
    US11117906B2|2018-12-21|2021-09-14|Colgate-Palmolive Company|Methods for synthesizing zinc-lysine-chloride complex|
    EP3897864A1|2018-12-21|2021-10-27|Colgate-Palmolive Company|Zinc-arginine-halide complex|
    法律状态:
    2018-10-16| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-02-05| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-07-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-10-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/12/2012, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US2012/070534|WO2014098828A1|2012-12-19|2012-12-19|Teeth whitening methods, visually perceptible signals and compositions therefor|comprising zinc amino acid halides|
    [返回顶部]